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This journal is c The Royal Society of Chemistry 2011 Chem. Soc. Rev.

Cite this: DOI: 10.1039/c1cs15078b

Graphene-based composites

Xiao Huang,a Xiaoying Qi,a Freddy Boeyab and Hua Zhang*ab

Received 28th March 2011

DOI: 10.1039/c1cs15078b

Graphene has attracted tremendous research interest in recent years, owing to its exceptional properties.

The scaled-up and reliable production of graphene derivatives, such as graphene oxide (GO) and reduced

graphene oxide (rGO), offers a wide range of possibilities to synthesize graphene-based functional

materials for various applications. This critical review presents and discusses the current development of

graphene-based composites. After introduction of the synthesis methods for graphene and its derivatives

as well as their properties, we focus on the description of various methods to synthesize graphene-based

composites, especially those with functional polymers and inorganic nanostructures. Particular emphasis

is placed on strategies for the optimization of composite properties. Lastly, the advantages of graphene-

based composites in applications such as the Li-ion batteries, supercapacitors, fuel cells, photovoltaic

devices, photocatalysis, as well as Raman enhancement are described (279 references).

1. Introduction

The direct observation and characterization of a mechanically

exfoliated graphene monolayer by Novoselov et al. in 20041

has sparked the exponential growth of graphene research in

both the scientific and engineering communities. Graphene, a

single-layer carbon sheet with a hexagonal packed lattice

structure, has shown many unique properties, such as the

quantum hall effect (QHE), high carrier mobility at room

temperature (B10 000 cm2 V1 s1),1 large theoretical specific

surface area (2630 m2 g1),2 good optical transparency

(B97.7%),3 high Youngs modulus (B1 TPa)4 and excellent

thermal conductivity (30005000 W m1 K1).5 To further

exploit these properties in various kinds of applications,

versatile and reliable synthetic routes have been developed

to prepare graphene and its derivatives, ranging from the

bottom-up epitaxial growth69 to the top-down exfoliation

of graphite by means of oxidation, intercalation, and/or

sonication.1013 In particular, the low-cost and mass production

of chemically exfoliated graphene oxide (GO)1429 and reduced

graphene oxide (rGO) sheets has been realized,1423,3034 which

possess many reactive oxygen-containing groups for further

functionalization and tuning properties of GO or rGO sheets.

With these added advantages, it is desirable to harness the

useful properties of graphene and its derivatives in composites,

through the incorporation with various kinds of functional

materials. To date, graphene-based composites have been

successfully made with inorganic nanostructures,1820,3538

organic crystals,3940 polymers,14,17,41,42 metalorganic frame-

works (MOFs),4345 biomaterials,4648 and carbon nanotubes

(CNTs),4953 and are intensively explored in applications such

as batteries,37,5456 supercapacitors,36,5759 fuel cells,6063

photovoltaic devices,19,33,64,65 photocatalysis,6669 sensing

platforms,46,47 Raman enhancement7072 and so on. In this

a School of Materials Science and Engineering, NanyangTechnological University, 50 Nanyang Avenue, Singapore 639798,Singapore. E-mail: [email protected], [email protected];Web: http://www.ntu.edu.sg/home/hzhang/

b Centre for Biomimetic Sensor Science, Nanyang TechnologicalUniversity, 50 Nanyang Drive, Singapore 637553

Hua Zhang

Hua Zhang studied at Nanjing

University (BS, MS), andcompleted his PhD at Peking

University (with Zhongfan Liu)

in 1998. After postdoctoral work

at Katholieke Universiteit

Leuven (with Frans De

Schryver) and Northwestern

University (with Chad Mirkin),

and working at NanoInk Inc.

(US) and the Institute of Bio-

engineering and Nanotechnology

(Singapore), he joined

Nanyang Technological Uni-

versity in July 2006. He was

promoted to a tenured associateprofessor in March 2011. He is an Associate Editor of the

International Journal of Nanoscience, on the Editorial Board of

NANO, and on the Advisory Committee of IOP Asia-Pacific.

His research interests focus on carbon materials (graphene and

CNTs) and their applications; controlled synthesis, characteri-

zation and application of novel nanomaterials; and surface

fabrication from the micro- to nanometre scale, etc. He has

published 25 patent applications, 3 book chapters, more than 130

papers with over 2400 citations and an H-index of 26. He has

been invited to give more than 70 Keynote Lectures and Invited

Talks in international conferences and universities, and serve as

Session Chair. He has organized several international confer-

ences and served as Symposium Chair.

Chem Soc Rev Dynamic Article Links

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Chem. Soc. Rev. This journal is c The Royal Society of Chemistry 2011

critical review, after introducing the properties and synthetic

methods of graphene and its derivatives, graphene-based

composites are discussed, with particular emphasis placed on

their fabrication/synthesis methods, properties and applications.

2. Properties of graphene

2.1 Electronic propertiesOne of the most important properties of graphene is that its

charge carriers behave as massless relativistic particles, or the

Dirac fermions.1 It has been demonstrated that graphene is a

zero-gap 2D semimetal with a tiny overlap between valence

and conductance bands, and charge carriers move with little

scattering under ambient conditions.1 It also exhibits a strong

ambipolar electric field effect with the concentration of charge

carriers up to 1013 cm2 and room-temperature mobilities of

B10000 cm2 V1 s1, when the gate voltage is applied.1

Besides, the suspended graphene shows low-temperature

mobility approaching 200 000 cm2 V1 s1 for carrier densities

below 5 109 cm2, which is not observable in semiconductors

or non-suspended graphene sheets.73 Additionally, an unusual

half-integer quantum Hall effect (QHE) for both electron and

hole carriers in graphene has been observed by adjusting the

chemical potential with the use of the electric field effect.74,75

Such QHE can be observed at room temperature as well,76 and

the fractional QHE was obtained when suspended graphene

devices were probed, which allows for the isolation of the

sample from substrate-induced perturbations.77

2.2 Optical properties

The measured white light absorbance of suspended single-

layer graphene is 2.3% with a negligible reflectance (o 0.1%),

and this absorbance increases linearly with the layer numbers

from 1 to 5.3 The measured values and the observed linearity

are in consistence with the theoretical calculation results

obtained with a model of non-interacting massless Dirac

fermions. It shows that the dynamic conductivity of graphene

in the visible range, G, only depends on the universal

constants, i.e. G E pe2/2h, where c is the speed of light, h is

Plancks constant.78 The transparency of graphene only

depends on the fine-structure constant a = 2pe2/hc, which

describes the coupling between the light and relativistic

electrons. The absorbance of n-layer graphene can thus be

simply expressed as npa. However, deviation from this

behavior is found with the incident photons with energy less

than 0.5 eV (or wavelength larger than B2480 nm), which is

attributed to the effects of finite-temperature, doping, and

intra-band transitions.79

The ultrafast optical pumpprobe spectroscopy has been

applied to study the carrier dynamics and relative relaxation

timescales of graphene layers grown on SiC.80 An initial fast

relaxation transient (70120 fs) followed by a slower relaxa-

tion process (0.41.7 ps) has been identified, which is asso-

ciated to the carriercarrier intra-band and carrierphonon

inter-band scattering process, respectively. With the help of

infrared spectroscopy, it is found that the inter-band transi-

tions and optical transitions of monolayer and double layer

graphene are layer-dependent and can be modulated through

the electrical gating, which holds promise for the infrared

optics and optoelectronics.81

2.3 Thermal properties

The thermal conductivity of single-layer suspended

graphene at room temperature has been measured as

30005000 W m1 K1 depending on the size of the measured

graphene sheet.5 It is supported on amorphous silica, a case

similar to the practical application, the measured thermal

conductivity of graphene is B600 W m1 K1, about one

order lower than that of the suspended graphene sheet.82 This

reduction in thermal conductivity is attributed to the leaking

of phonons across the graphenesilica interface and strong

interface-scattering. Nevertheless, this value is still about

2 times and 50 times higher than copper and silicon, respec-

tively, which are used in the electronics today.

2.4 Mechanical properties

The intrinsic mechanical properties of free-standing mono-

layer graphene membranes were measured based on the

nanoindentation using atomic force microscopy (AFM).

4

The breaking strength is 42 N m1 and the Youngs modulus

is 1.0 TPa, suggesting the strongest material ever measured.

Theoretical work has been carried out to investigate the

mechanical properties of zigzag graphene and armchair graphene

nanoribbons, suggesting that the critical mechanical loads for

failure and buckling of armchair ribbons are smaller than

those for zigzag ribbons.83 In addition, external mechanical

loads can change the electronic properties of graphene, such as

field emission performance.83,84 By employing a cantilever

beam, single-layered graphene can be subjected to various

degrees of axial compression.85 The uptake of stress and the

compression buckling strains of different geometries have thus

been measured. It is found that the mechanical response isrelated to the Raman shift of the G or 2D phonons of graphene.

The elastic deformation of functionalized graphene sheets

(FGSs), or chemically reduced graphene oxide (rGO), has also

been studied by AFM.86 After repeatedly folding and unfolding

of the FGSs multiple times, the folding lines were found to

appear at the same locations, which can be attributed to the

pre-existing kinks or defect lines in the FGSs.

3. Synthetic methods

Till now, tremendous efforts have been made to develop

synthetic methods for graphene and its derivatives, not only

to achieve high yield of production, but also to realize the

solution or thin film based process. These methods can be

generally classified as the bottom-up and top-down approaches.

Table 1 summarizes and compares the typical synthetic

methods for graphene and its derivatives. The bottom-up

approach involves the direct synthesis of graphene materials

from the carbon sources, such as the chemical vapor deposition

(CVD), which is a typical method used to grow large-area,

single and few-layer graphene sheets on metal substrates, e.g.

Ni, Ru, and Cu.69,49 Plasma enhanced CVD (PECVD) is able

to grow single-layer graphene with high throughput at shorter

reaction time and lower deposition temperature compared to

the CVD process.87 Besides, graphitization of carbon-containing

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substrates, such as SiC, can give rise to single-layer and

few-layer graphene films as well through the high temperature

annealing.88,89 In addition to these methods based on the

solid-phase deposition, graphene is also obtainable via the

wet chemical reaction of ethanol and sodium followed by

pyrolysis,90 or through the organic synthesis to give graphene-

like polyaromatic hydrocarbons.91,92

Different from the bottom-up approaches, the top-down

approaches are advantageous in terms of high yield, solution-

based processability, and ease of implementation, which have

been demonstrated by means of intercalation, chemical func-

tionalization, and/or sonication of bulk graphite. The first

observation of exfoliated graphite dates back to 1840 by

Schafhaeutl, when H2SO4 was used for the intercalation.93

Since then, a number of chemical species have been found to

form intercalated compounds with graphite.9497 Further

attempts, combining the intercalation and sonication, have

realized isolation and dispersion of graphene sheets by using

intercalates such as N-methyl-pyrrolidone (NMP)11 and

sodium dodecylbenzene sulfonate (SDBS)13 in non-aqueous

and aqueous solutions, respectively. Re-intercalation of

thermally exfoliated expandable graphite (EG) with oleum

(fuming sulfuric acid with 20% free SO3) and tetrabutyl-

ammonium hydroxide (TBA) has also produced single-layer

graphene sheets with a yield of B90% after purification.98

Even without sonication, ternary potassium salt-intercalated

graphite readily gives isolated graphene sheets in NMP.12

Additionally, electrochemical exfoliation of graphite has also

achieved graphene nanosheets in ionic liquids.99 Unfortu-

nately, the aforementioned methods face drawbacks such

as the low yield of single-layer production,13 expensive

intercalates,11 and residual surfactant induced low conductivity.

Therefore, an alternative approach, the reduction of highly

oxidized graphene oxide (GO) sheets from the exfoliated

Table 1 Comparison of various methods for preparation of graphene and its derivatives

Methods Conditions Yield and properties Ref.

Bottom-up approachesCVD Carbon sources: CH4, H2 Sheet size of up to a few tens of micrometres. 68

Substrate: Ni, Ru, CuTemperature: 1000 1C

PECVD Carbon source: CH4, H2 Large area of more than 1 cm of monolayergraphene

87Substrate: Cu

Temperature: 650 1CGraphitization Substrate: 6H-SiC(0001) Grain size: up to 50 mm long, 1 mm wide 89

Temperature: 1280 1CSolvothermal Reagents: Na and ethanol Folded graphene structures 90

Temperature: 220 1C Bulk conductivity: B0.05 S m1

Organic synthesis Thermal fusion of polycyclic aromatichydrocarbons at 1100 1C

For a 30 nm thick film on quartz, conductivity:20600 S m1, sheet resistance: 1.6 kO m2

91

Top-down approachesLiquid exfoliation ofgraphite

Intercalate: NMP Single-layer yield: 712 wt% after purification 11Film conductivity: B6500 S m1

Intercalate: SDBS Film conductivity: B35 S m1 13Single-layer yield: B3% with a size ofB1 mm

Intercalate: ternary potassium salt Graphene ribbons with lengths ofB40 mm. 12Thermal exfoliation andliquid intercalation

Thermal exfoliation at 1000 1C Single-layer yield: B90% after purification 98Intercalates: oleum and TBA Size: B250 nm

Resistance of single sheet with 100 nm in width:1020 kO

Electrochemicalexfoliation

1-Octyl-3-methyl-imidazolium hexafluoro-phosphate as electrolyte; graphite rods as electrodes

Sheet size: 500 700 nm 99

Chemical reductionof GO

Reduction agent: hydrazine Sheet resistance of graphene paper: 7200 S m1 31Deoxygenation agent: KOH or NaOH Incomplete removal of oxygen-containing groups 109Temperature: 5090 1CReduction agent: bovine serum albumin To be used as template for nanoparticle synthesis 111Reduction agent: vitamin C Film conductivity: up to 7700 S m1 133Temperature: 95 1CReduction via bacteria respiration Film resistance decreased up to 104 after reduction 134Reduction agent: hydriodic acid and acetic acid Sheet resistance: pellets dried after solution

reduction: 30 400 S m132

In solution at room temperature or in vaporat 40 1C

Thin film after vapor reduction: 7850 S m1

Sonolytic reduction: ultrasonication at 211 kHzfor 30 min

Formation of 14 layers of rGO 127

Microwave-assisted reduction in the presence of

hydrazine

Formation of 18 layers of rGO with size up to a

few micrometres

128

Thermal reductionof GO

220 1C in air for 24 h Film sheet resistance: 8 kO sq1 124

150 1C in DMF for 1 h Film resistance: 6 kO 119Photothermal reductionof GO

High pressure Hg lamp with H2 or N2 flow Sheet size: B1 um 115Single-sheet conductivity: 200020000 S m1

Pulsed xenon flash Able to prepare a GO/rGO patterned film with aphotomask

126

Sheet resistance of rGO area: B9.5 kO sq1

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graphite oxide has been developed,10 and mostly employed to

prepare reduced GO (rGO), chemically converted graphene

(CCG), or functionalized graphene sheets (FGS). The graphite

oxide is obtained by the Hummers method via the reaction of

graphite with a mixture of potassium permanganate (KMnO4)

and concentrated sulfuric acid (H2SO4).1423 The exfoliated

GO sheets are thus highly oxidized and featured with the

residual epoxides, hydroxides and carboxylic acid groups on

their surfaces.100,101 So far, various types of reduction methods

have been reported to obtain rGO sheets, such as the chemical

reagent reduction,1422,31,33,102112 photochemical reduction,113116

thermal reduction,117124 photothermal reduction,125,126

sonolysis,127 microwave-assisted reduction128 and electro-

chemical reduction.129132 Among these methods, the chemical

reduction is the most versatile one with many reduction agents

being used, such as hydrazine,1422,31,33,102108 strong alkaline

media,109 vitamin C or ascorbic acid,110,133 bovine serum

albumin (BSA),111 bacterial respiration,134 and hydriodic

acid.32,135 To date, the rGO sheets reduced by hydriodic acid

and acetic acid have shown the best electronic conductivity

(up to 30000 S m1).32 Due to the less toxicity of hydriodic

acid, this method is expected to replace the hydrazine

reduction for the mass production of rGO dispersions and

fabrication of rGO thin films. Despite the fact that the

conductivity of rGO is orders lower compared to the pristine

graphene due to the presence of residual oxygenated groups

and defects, the reactive surfaces of GO and rGO provide the

tunability in electronic and optoelectronic properties via

chemical reactions,118,136,137 and the feasibility for composite

incorporation.138

4. Grapheneinorganic nanostructure composites

In the last few decades, huge efforts have been made to

synthesize inorganic nanostructures with controlled shape,

size, crystallinity and functionality. These materials are widely

employed in applications like electronics, optics, electro-

chemical energy conversion and storage, solar energy harvesting,

and so on. In order to further enhance their properties, a great

number of inorganic nanostructures have been composited

with graphene and its derivatives, which include metals like

Au,20,35,111,114,127,139146 Ag,20,146150 Pd,128,141,146,151,152

Pt,111,141,146,153 Ni,154 Cu,128 Ru155 and Rh;155 oxides like

TiO2,67,68,113,156162 ZnO,19,163165 SnO2,

166,167 MnO2,168,169

Co3O4,54,55,170,171 Fe3O4,

172175 NiO,176 Cu2O,18,102,177

RuO2,59 and SiO2;

178 chalcogenides like CdS179182 and

CdSe.183,184 The fabrication methods are generally classified

as the ex situ hybridization, and in situ crystallization. Table 2

has summarized the typical synthetic methods for graphene

inorganic nanostructure composites and their related applications.

4.1 Ex situ hybridization

The ex situ hybridization involves the mixture of graphene-

based nanosheets and pre-synthesized or commercially

available nanocrystals in solutions. Before mixing, surface

modification of the nanocrystals and/or graphene sheets is

often carried out, so that they can bind through either the

non-covalent interactions or the chemical bonding. For example,

2-mercaptopyridine modified Au nanoparticles (NPs)145 or

benzyl mercaptan-capped CdS NPs179 have been successfully

attached to GO or rGO surfaces via the pp stacking. Alter-

natively, rGO sheets can be modified with adhesive polymers

for anchoring the NPs, which has been demonstrated in the

Nafion-coated rGO/TiO2 composites.161 Amphiphilic bio-

polymers, such as bovine serum albumin (BSA) protein, have

also been used to modify the rGO surface via the pp inter-

action, which then serve as a universal adhesive layer to

absorb Au, Ag, Pt and Pd NPs.146

Instead of decorating NPs on GO/rGO surfaces, GO/rGO

sheets can wrap around the oxide NPs for specific applications

such as the Li-ion battery.55 As reported, after the positively

charged SiO2 or Co3O4 NPs (modified by aminopropyl-

trimethoxysilane, APS) are encapsulated by negatively

charged GO sheets through the electrostatic interaction, the

GO can be in situ reduced to rGO subsequently without

destroying the sheet-encapsulated-particle structures.

4.2 In situ crystallization

Although the ex situ hybridization is able to pre-select nano-

structures with desired functionalities, it sometimes suffersfrom the low density and non-uniform coverage of the nano-

structures on the GO/rGO surfaces.145 In contrast, the in situ

crystallization can give rise to uniform surface coverage of

nanocrystals by controlling the nucleation sites on GO/rGO

via surface functionalization. As a result, the continuous film

of NPs on graphene surfaces can be realized.

4.2.1 Chemical reduction method. Chemical reduction is

the most popular strategy for synthesis of metal nano-

structures. Precursors of noble metals, such as HAuCl4,

AgNO3, K2PtCl4 and H2PdCl6, can be simply in situ reduced

by reduction agents like amines, NaBH4, and ascorbic acid.

For example, grapheneAu NP composites can be obtained by

the reduction of HAuCl4 with NaBH4 in a rGO-octadecyl-

amine (ODA) solution.35 However, since rGO contains much

less residual oxygen-containing functional groups than GO, it

is restricted to aqueous solution based processes. To address

this problem, 3,4,9,10-perylene tetracarboxylic acid (PTCA)-

modified rGO sheets have been used as templates for the in situ

reduction of HAuCl4 with amino-terminated ionic liquid

(IL-NH2). Because of the additional carboxylic groups from

PTCA, the resulting rGOAu NP composites are water soluble

and give a dense coverage of NPs.139

Anisotropic metal nanostructures, such as nanorods143,185

and snowflakes,142 have also been synthesized on rGO or GO

surfaces via chemical reduction. For example, Au nanorods

can be prepared on rGO films or seed-modified rGO films, by

using a shape-directing surfactant, cetyl trimethylammonium

bromide (CTAB), to facilitate the one dimensional growth of

the nanorods. Very recently, by using GO as a synthetic

template, we have synthesized square-like Au nanosheets with

an edge length of 200500 nm and a thickness of B2.4 nm

(Fig. 1A).38 These Au nanosheets display the unique hexa-

gonal close packed (hcp) structure. This is the first time to

directly synthesize hcp Au nanostructures by the wet chemical

method.

Besides the single-phased metal structures, Pt-on-Pd bimetallic

nanodendrites on polyvinylpyrrolidone (PVP)-modified rGO

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sheets have been synthesized in a seed-mediated sequential

process, where the Pd seeds were synthesized on rGO by the

reduction of H2PdCl4 with HCOOH, and then Pt nano-

dendrites on the Pd seeds were formed by reducing K2PtCl4with ascorbic acid (Fig. 1B).186 In this work, the pre-synthetic

functionalization of rGO with PVP has provided good

solubility of the rGO sheets in aqueous solution, and high

nucleation density of the Pd seeds.

As an alternative, the photochemical reduction has also

been applied for synthesis of graphenemetal nanostructure

composites.114,187 For example, our group has synthesized the

fluorescent Au nanodots (NDs, with sizeo2 nm) on thiol-modified

GO/rGO surfaces by simply in situ reducing HAuCl4 under

light irradiation.114 Especially, if octadecylthiol (ODT) is used

to modify the rGO surfaces, the in situ synthesized Au NDs

self-assemble into short ND-chains on the ODT-rGO surfaces

(Fig. 1C), along the h100i direction of the graphitic lattice.

This is due to the specific pattern formation of the long chain

thiol molecules on the rGO surface, which in turn serves as a

secondary template for the synthesis and self-assembly of Au

NDs. In another approach, semiconductor nanoparticles

loaded on GO/rGO sheets are employed to catalyze the

reduction of metal ions. The excited state interaction

between semiconductor and GO/rGO has been studied in

Table 2 Comparison of typical synthetic methods for grapheneinorganic nanostructure composites and their related applications

Materials Synthetic routes Applications Ref.

Au/GO or rGO Ex situ: pp stacking via 2-mercaptopyridine Catalysis, SERS 145Ex situ: pp stacking via bovine serum albumin 146In situ: photochemical reduction 114In situ: reduction by hydroxyl-amine Raman enhancement 142In situ: sonolytic reduction in poly(ethylene glycol) at 211 kHz 127

Au/rGO In situ: reduction by NaBH4 Plasmonics 35

In situ: reduction by amino terminated ionic liquid; perylene-modified rGO Electrocatalysis 139In situ: reduction by sodium citrate SERS 144In situ: reduction by ascorbic acid in the presence of CTAB Raman enhancement 185In situ: microwave assisted reduction 128,190

Au/pristine graphene In situ: thermal evaporation Identification of layer numberof pristine graphene

189

Ag/GO or rGO Ex situ: pp stacking via bovine serum albumin 146In situ: reduction by NaBH4 150In situ: electroless deposition SERS 20

Ag/TiO2/rGO In situ: Ag is reduced by the photo-generated electrons from TiO2/rGO 187Ag/rGO In situ: microwave assisted reduction 128Pt or Pd/GO or rGO Ex situ: pp stacking via bovine serum albumin 146Pd/rGO In situ: microwave assisted reduction 128Pt-on-Pd/rGO In situ: sequential reduction of H2PdCl4 with HCOOH, and K2PtCl4

with ascorbic acidEletrocatalysis 186

Cu/rGO In situ: microwave assisted reduction 128Ru/rGO In situ: microwave assisted reduction Catalysis 155Rh/rGO In situ: microwave assisted reduction Catalysis 155CdS/rGO Ex situ: pp stacking via benzyl mercaptan Optoelectronics 179TiO2/GO Ex situ: non-covalent adhesion via solution mixing of P-25 TiO2 and GO DSSC 156

Ex situ: non-covalent adhesion via solution mixing with the GO film Photocatalysis 158TiO2/rGO Ex situ: noncovalent adhesion via Nafion DSSC 161

Ex situ: self-assembly of TiO2 nanorods and rGO at two-phase interface Photocatalysis 67In situ: templated hydrolysis starting with TiCl3 and titanium isopropoxide Photocatalysis 68In situ: hydrolysis starting with TiCl3 Li ion battery 157In situ: hydrolysis starting with titanium butoxide DSSC 160In situ: hydrothermal starting with P25 and GO Photocatalysis 162

ZnO/rGO In situ: electrochemical deposition Photovoltaics 19Cu2O/rGO In situ: electrochemical deposition Photovoltaics 18Cl-doped Cu2O/rGO In situ: electrochemical deposition Optoelectronics 102Co3O4/GO or rGO Ex situ: electrostatic via aminopropyltrimethoxysilane Li ion battery 55

In situ: reduction of Co(OH)2/GO at 450 1C Li ion battery 54Co3O4/rGO In situ: microwave assisted reaction between urea and Co(NO3)2 Supercapacitor 170

MnO2/GO In situ: redox reaction between MnCl2 and KMnO4 Supercapacitor 168In situ: microwave assisted reaction between C and KMnO4 Supercapacitor 169

MnO2/FGS In situ: redox reaction between Na2SO4 and KMnO4 Li ion battery 166SiO2/GO or rGO Ex situ: electrostatic via aminopropyltrimethoxysilane 55SiO2/FGS In situ: hydrolysis starting with TEOS 166SnO2/FGS In situ: redox reaction starting with SnCl2 and H2O2 Li ion battery 166Fe3O4/rGO In situ: hydrolysis starting with FeCl3 Li ion battery 173Fe3O4/GO In situ: redox reaction starting with FeCl2, FeCl3 and NaOH Magnetic drug carrier 175

In situ: reaction of ferric triacetylacetonate with GO in 1-methyl-2-pyrrolidone Magnetic composite 172NiO/graphene In situ: sputtering Nanocapacitor 176RuO2/rGO In situ: redox reaction starting with RuCl3 and GO Supercapacitor 59CdS/rGO In situ: chemical bath deposition Solar cell 180CdS/rGO In situ: hydrothermal starting with dimethylsulfoxide, GO and Cd(CH3COO)2 Optoelectronics 181CdSe/CVD-graphene In situ: electrochemical deposition templated by a porous silica film Optoelectronics 183

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the GO/ZnO system, based on the photoluminescence decay

measurements.165 It is shown that the lifetime of ZnO

emission is decreased in the presence of GO sheets, indicating

the fast electron transfer from ZnO to GO with a transfer-rate

constant of 1.2 109 s1. Such rapid electron transfer between

semiconductor nanoparticles and GO/rGO makes their

composites attractive photocatalysts. As an example, after

GO sheets are photocatalytically reduced in the presence of

light-excited TiO2 nanoparticles, the resulting rGO/TiO2hybrid catalyst is subsequently used for photo-reduction of

Ag+. During this process, the photo-generated electrons from

TiO2 are rapidly captured by rGO and then transferred to

reduce the absorbed Ag+ ions on the rGO surface.187

In addition to metals, metal oxides, such as RuO2,54 SnO2

166

and MnO2,168 can also form on GO/rGO surfaces via in situ

reduction/oxidation. For example, GO/RuCl3

was heated with

a hot soldering iron in a N2 atmosphere and in situ reduced to

rGO/RuO2 nanocomposites,54 and KMnO4 reacting with

MnCl24H2O in the presence of GO sheets has led to

MnO2GO composites.168

Microwave irradiation is a rapid and facile method to

provide energy for chemical reactions. It can be used for the

simultaneous formation of metal NPs (e.g. Cu, Pd, Au

and Ag)128 and reduction of GO. Additionally, the in situ

microwave irradiation has been used to prepare metal oxide

rGO hybrids, such as rGOMnO2 NPs169 and rGOCo3O4

NPs.170 In the former work, rGO serves as the carbon source

to react with KMnO4 under microwave irradiation to form

CO23 , HCO

3 , and MnO2.169 In spite of the ease of process

and scalable production, the aforementioned microwave-

assisted syntheses did not show the fine control over the size

uniformity and surface distribution of NPs on rGO surfaces.

More recently, the microwave irradiation was combined with

ironic liquid (IL)-assisted dispersion of rGO to make Ru/rGO

and Rh/rGO composites, which exhibit densely loaded Ru or

Rh NPs with narrow size distributions of 2.20.4 nm and

2.80.5 nm, respectively.155

4.2.2 Electroless deposition. The electroless deposition of

metals has been previously observed on single-walled carbon

nanotubes (SWCNTs), where Au and Pt NPs formed on the

side-walls of SWCNTs immediately after immersing the

SWCNTs in solution of HAuCl4 or Na2PtCl2.188 Because

the Femi level of SWCNT is higher (less negative) than the

redox potential of Au or Pt, the SWCNT serves as the

cathode to donate electrons for the nucleation of metal

NPs. Based on the similar mechanism, we have shown that GO

can be used to template the growth of Ag nanostructures via

the electroless deposition, by simply heating GO films

deposited on APTES-modified Si/SiOx substrates in AgNO3solutions.20 In addition to GO, rGO sheets can also lead to the

formation of Ag NPs due to the presence of many aromatic

conjugated domains for electron donation. Importantly, the

abundant residual oxygen-containing groups on GO provide

more nucleation sites for metal nucleation, thus resulting in

formation of smaller Ag NPs with higher density compared to

using rGO as the template in the electroless deposition.

4.2.3 Solgel methods. The solgel process is a popular

approach for preparation of metal oxide structures and film

coatings, with the metal alkoxides or chlorides as precursors

that undergo a series of hydrolysis and polycondensation

reactions. It has been used to in situ prepare TiO2,68,157,160

Fe3O4173 and SiO2

166 nanostructures on FGS (or rGO) sheets.

Taking TiO2 as an example, the typical precursors used are

TiCl3,157 titanium isopropoxide,68 and titanium butoxide,160

which have resulted in nanorods, NPs, or macromesoporous

framework of TiO2 depending on the different experimental

conditions applied. The key advantage of the in situ solgel

process lies in the fact that the surface OH groups of the

GO/rGO sheets act as the nucleation sites for the hydrolysis,

so that the resulting metal oxide nanostructures are chemically

bonded to the GO/rGO surfaces.

4.2.4 Hydrothermal methods. Hydrothermal is a powerful

tool for synthesis of inorganic nanocrystals, which operates at

elevated temperatures in a confined volume to generate high

pressure. The one-pot hydrothermal process can give rise to

nanostructures with high crystallinity without post-synthetic

annealing or calcination, and at the same time reduce GO

to rGO. Typically, TiO2rGO composites162 and CdSrGO

composites have been prepared by the hydrothermal process.

For example, after the mixture of GO and Cd(CH3COO)2in dimethylsulfoxide (DMSO) was heated in an autoclave at

180 1C for 12 hours,181 the simultaneous reduction of GO to

rGO and the formation of CdS NPs were realized, with the

DMSO acting as both the solvent and the sulfur source.

Fig. 1 (A) TEM image of Au square sheets synthesized on GO.

Reproduced from ref. 38. (B) TEM image of solution-synthesized

Pt-on-Pd nanodendrites on rGO. Reproduced with permission from

ref. 186. Copyright 2009, American Chemical Society. (C) TEM image

of ordered Au NDs photochemically synthesized on rGO. Reproduced

with permission from ref. 114. Copyright 2010, John Wiley & Sons,

Inc. (D) TEM image of ordered CdSe NPs electrochemically deposited

on a graphene sheet. Reproduced with permission from ref. 183.

Copyright 2010, John Wiley & Sons, Inc.

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4.2.5 Electrochemical deposition. Direct electrochemical

deposition of inorganic crystals on graphene-based substrates,

without the requirement for post-synthetic transfer of the

composite materials, is an attractive approach for thin film-

based applications. Nanostructures of ZnO, Cu2O and

CdSe18,19,183 have been successfully deposited on rGO or

CVD-graphene films. As an example, ZnO nanorods have

been deposited on spin-coated rGO thin films on quartz, by

using oxygen saturated aqueous solution of ZnCl2 and KCl as

the electrolyte.19 This method has also been extended to

deposit Cu2O nanostructures18 as well as Cl-doped n-type

Cu2O102 on rGO films, spin-coated on flexible polyethylene

terephthalate (PET) substrates. In addition to the random

deposition of nanostructures on rGO films, ordered nano-

structure patterns can also be prepared by electrochemical

deposition using porous template.183 As reported, a layer of

mesoporous silica film was first formed on the CVD-grown

graphene sheets via a solgel process, and then CdSe NPs were

electrochemically deposited on the graphene surface through

the pores of the pre-coated silica film. After removing the silica

film by HF etching, ordered CdSe NPs on graphene are

revealed (Fig. 1D).

4.2.6 Thermal evaporation. The thermal evaporation has

been utilized to deposit Au NPs on the pristine graphene and

how the layer number of graphene affects the particle size and

density of deposited Au NPs has been studied.189 It is found

that the particle density increases and size decreases with

increasing the layer number of graphene. This interesting

phenomenon has been attributed to two factors. First, the

diffusion coefficient of deposited Au atoms varies on different

surfaces, which governs the nucleation and growth of the Au

islands. Second, the surface free energy of graphene depends

on the layer number, which controls the interaction between

graphene and the evaporated Au atoms, and in turn affects the

surface absorption, desorption and diffusion of the Au atoms

on graphene surface.189

4.2.7 Ordered metal oxidegraphene composites via in situ

self-assembly. In contrast to the random stacking of graphene-

based hybrid nanosheets, a novel method has been developed

to prepare the ordered metal oxidegraphene hybrids by the

surfactant assisted self-assembly.166 In this work, the anionic

surfactants were first mixed with rGO sheets, which attached

to the hydrophobic domains of the surfactant micelles

(Fig. 2A). After that, metal cations were introduced and

bonded to the surfactants assembled on rGO, to give an

ordered overall structure (Fig. 2B). In situ crystallization then

took place, via redox or hydrolysis reactions, to result in the

alternating layers of rGO/metal oxides, e.g. NiO, SnO2, and

MnO2 (Fig. 2C and D). This assembly process is important

in constructing layered composite materials for lithium ion

batteries, which will be discussed in section 7.1.

5. Graphenepolymer composites

The graphenepolymer composites, based on the 3D arrange-

ment and the kind of interaction between graphene sheets and

polymers, can be classified into three types, i.e. graphene-filled

polymer composites, layered graphenepolymer films, and

polymer-functionalized graphene nanosheets.

5.1 Graphene-filled polymer composites

Carbon-based materials, such as amorphous carbon and

carbon nanotubes (CNTs), are conventional fillers for enhancing

the electronic, mechanical and thermal properties of polymer

matrices. CNT has been regarded as one of the most effective

filler materials, but with relatively high cost. Graphene-based

fillers are thus expected as a promising replacement or supple-

ment to CNTs. In order to lower the content of the graphene

filler, the dispersity and its bonding with the polymer matrix are

important factors to achieve optimal properties of the compo-

sites. With this consideration in mind, graphene-filled polymer

composites are commonly prepared by solution mixing,42,191195

melt blending,196198 and in situ polymerization.199210

5.1.1 Fabrication methods. Solution mixing is the most

straightforward method for preparation of polymer compo-

sites. The solvent compatibility of the polymer and the filler is

critical in achieving good dispersity. Due to the residual

oxygen-containing functional groups, GO can be directly

mixed with water soluble polymers, such as poly(vinyl alcohol)

(PVA), at various concentrations.191,211 However, GO does

not dissolve in non-polar solvents, and other forms of

graphene such as expanded graphite (EG) and rGO show

limited solubility in both organic and inorganic solvents. In

order to overcome this problem, sonication has been used to

Fig. 2 (AC) Schematic illustrations of the self-assembly approach to

prepare ordered metal oxide/rGO composites. (A) Adsorption of

surfactant hemimicelles on the surfaces of the rGO or rGO stacks

causes its dispersion in surfactant micelles in an aqueous solution. (B)

The self-assembly of anionic sulfonate surfactant on the graphene

surface with oppositely charged metal cation (e.g. Sn2+) species and

the transition into the lamella mesophase toward the formation ofSnO2 graphene nanocomposites, where hydrophobic rGO sheets are

sandwiched in the hydrophobic domains of the anionic surfactant. (C)

Layered metal oxiderGO composites composed of alternating layers

of metal oxide nanocrystals and rGO stacks after crystallization of

metal oxide and removal of the surfactant. (D) High-magnification

TEM of SnO2/rGO composites. The layered structure of SnO2 is

composed of connected nanocrystalline SnO2 with 45 nm diameter

interspaced by rGO stacks. Reproduced with permission from ref. 166.

Copyright 2010, American Chemical Society.

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produce metastable dispersions of graphene derivatives, which

are then mixed with polymer solutions, such as those of

poly(methyl methacrylate) (PMMA),192 polyaniline (PANi),195

polycaprolactone (PCL),193 and polyurethane (PU).194,212

High-speed shearing combined with ice-cooling has also been

applied to mix graphene-based fillers and the polymer

matrices.42 However, in the two approaches mentioned above,

re-stacking, aggregation and folding of the graphene based

nanosheets are unavoidable during the process, which signifi-

cantly reduce the specific surface area of the 2D fillers. Thus,

surface functionalization of graphene-based fillers before

solution mixing must be carried out to provide them with

good solubility in various kinds of solvents. As an example,

phenyl isocyanate-modified GO sheets have shown improved

dispersity in polystyrene (PS) solution in DMF. During the

subsequent in situ reduction of GO, the polymer matrix

prevents the re-aggregation of rGO sheets to retain a homo-

geneous suspension.138

Melt compounding utilizes both high-shear forces and high-

temperature melting to blend the filler and matrix materials.

Hence, it does not require a common solvent for the graphene

filler and the polymer matrix. Polylactide (PLA)-exfoliated

graphite (EG) composite 196 and PETrGO graphene composite197

were successfully prepared by using melt compounding.

However, the high shear forces employed in melt compounding

can sometimes result in the breakage of the filler materials,

such as CNTs and graphene nanosheets.198

In situ polymerization is another often used method to

prepare graphene-filled polymer composites, such as those

with epoxy199201,213 and polyaniline (PANi).202206 In a

typical process for preparation of grapheneepoxy composite,

after the graphene based filler is mixed with epoxy resins under

high-shear forces, a curing agent is added to initiate the

polymerization.199 The polymerization for PANi, on the

other hand, is an oxidative process, thus an oxidative agent,

such as ammonium persulfate, is used to facilitate the

polymerization.204 Alternatively, graphenePNAi composite

can be prepared by the in situ anodic electropolymerization.207

For example, PANi has been directly deposited on the

working electrode made from graphene paper in a three-

electrode cell, with a solution containing aniline monomers

as the electrolyte. In addition to the epoxy and PANi,

graphene has been successfully incorporated in other polymer

matrices, such as silicone,208 PS209 and poly(vinyl chloride/

vinyl acetate) copolymer,210 via the in situ polymerization.

5.1.2 Property enhancement. Electrical conductivity has

shown significant improvement in graphene-filled polymers.

Very low percolation thresholds have been achieved in various

types of insulating matrices, for example, 0.15 vol% loading of

rGO in poly(vinyl chloride/vinyl acetate) copolymergraphene

composites,210 0.47 vol% filler loading in PETgraphene

composites (with a conductivity of 2.11 S m1 obtained at

a loading of 3.0 vol%),197 and 0.1 vol% filler loading in

PS-functionalized graphene sheets (FGS) composites.138

The effective property enhancement in these reports has

been attributed to the large specific surface area and the

p-conjugated 2D conducting surface of graphene-based

sheets, their homogeneous dispersion in the polymer matrix,

and the fillermatrix interaction induced by the surface func-

tional groups.

Besides the electrical conductivity, graphene-based fillers

can improve the mechanical strength of the polymer as well,

since the monolayer graphene is one of the strongest materials

with a Youngs modulus of 1.0 TPa and a breaking strength of

42 N m1.4 By using solution mixing and vacuum filtration,

the strong and ductile poly(vinyl alcohol)(PVA)GO compo-

site paper has been prepared, which shows a Youngs modulus

of 4.8 GPa and a tensile yield strength ofB110 MPa with

3 wt% of the GO loading. Unfortunately, in the physically

mixed composite, the relative movement between the filler and

matrix cannot be avoided under external stresses, which limits

the achievable maximum strength. To alleviate or solve this

problem, it is necessary to chemically tailor the structure at the

filler/matrix interface to facilitate the efficient load transfer.

For example, GO filler was covalently bonded to isocyanated-

PU matrix via the reaction between the oxygenated groups of

GO and the isocyanate groups at the end of PU chains. This

chemical bonding has led to the increase in the Youngs

modulus and hardness byB900% andB327%, respectively.194

The thermal stability is another important property for

functional polymers, which can be improved by embedding

materials with superior thermal properties like the graphene-

based fillers. For example, FGSPMMA composite gives an

increase of 30 1C in Tg (glass transition temperature, above

which chains of thermoplastic polymer begin to flow) with a

loading of 0.05 wt% FGS, whereas the Tg of poly(acrylonitrile)

(PAN)FGS composite increases more than 40 1C with a

loading of 1 wt% FGS,42 which surpasses all other carbon-

based nanofillers, such as the expanded graphite (EG) and the

graphitic nanoplatelets (GNPs).192 The superior performance

of FGSs fillers, arises from the presence of larger amount of

monolayer graphene sheets with wrinkled morphology and

functionalized surfaces, which benefits the strong fillermatrix

interaction (Fig. 3A and B).42 Besides the thermoplastics,

graphene-filled elastomers also exhibit enhanced thermal

stability in terms of increased degradation temperature.

Examples include the siliconeFGS composites with a 55 1C

increase in the degradation temperature with 0.25 wt%

loading of the filler,208 and the PLAEG composite with the

degradation temperature improved by 10 1C with a loading of

only 0.5 wt% of EG.196

Furthermore, the graphene-based filler materials have also

enhanced the thermal conductivity of polymer matrices, provided

that the single layer graphene has a thermal conductivity

of up toB5000 W mK1 at room temperature.214 When only

Fig. 3 SEM images of (A) EGPMMA and (B) FGSPMMA showing

fracture surface topography. Reproduced with permission from

ref. 42. Copyright 2008, Nature Publishing Group.

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0.25 wt% of FGSs were incorporated in the silicon foam

matrix, the increase of 6% in the thermal conductivity was

obtained.208 In addition, epoxy with embedded few-layer

graphene sheets (B25 vol%, layer number of B4) has

displayed an increase in the thermal conductivity of more

than 30 times at k = 6.44 W mK1.199 This result outperforms

many conventional fillers, such as Al, Ag and SiO2, which

require more than 50% loading to achieve the similar result.

5.2 Layered graphenepolymer films

In contrast to the graphene-filled polymer composites, where

the graphene fillers are randomly distributed in the polymer

matrices, graphene derivatives have also been composited with

polymers in layered structures, which are fabricated for

specific applications, such as the directional load-bearing

membranes, and thin films for photovoltaic applications.

For example, layer-by-layer (LbL) assembling via the

LangmuirBlodgett (LB) technique has been used to deposit

GO sheets onto films of polyelectrolyte poly(allylamine

hydrochloride) (PAH) and poly(sodium 4-styrene sulfonate)

(PSS) multi-layers (Fig. 4A).215 The resulting compositedmembrane shows enhanced directional elastic modulus by an

order of magnitude, i.e. from 1.5 to 20 GPa with 8 vol%

loading of the graphene (Fig. 4B). The similar strategy has

been used to prepare multi-layer PVAGO films, which also

display improved elastic modulus and hardness.216 Another

application that requires layered graphenepolymer compo-

sites is in polymer-based photovoltaic devices.217219 These

composite films are fabricated by the sequential spin-coating

of functional components in the device configurations. For

example, GO film and poly(3-hexylthiophene) (P3HT)/phenyl-

C61-butyric acid (PCBM) blends are deposited layer after

layer on ITO substrate, where the GO layer acts as the hole

transport segment in the photovoltaic device.218

5.3 Polymer functionalized graphene nanosheets

Instead of being used as fillers to enhance the properties of

polymers, graphene derivatives can be applied as 2D templates

for polymer decoration via covalent and non-covalent functio-

nalizations. The polymer coating, on the other hand, assists to

improve the solubility of the graphene derivatives, and offers

additional functionality to the resulting hybrid nanosheets.

The covalent functionalization of graphene derivatives is

mainly based on the reaction between the functional groups

of the polymers and the oxygenated groups on the GO or rGO

surfaces. Esterification of the carboxylic groups in GO with the

hydroxyl groups in PVA has been demonstrated in the synthesis

of GOPVA composite sheets.220 The carboxylic groups on GO

were also involved in the carbodiimide-catalyzed amide forma-

tion process to bind with the six-armed polyethylene glycol

(PEG)-amine stars.221 However, the carboxylic groups are

mainly confined at the periphery of the GO sheets. In addition,

the grafting of certain polymers requires the presence of

non-oxygenated functional groups on GO, such as amine and

chloride groups. Therefore, alternative strategies with addi-

tional chemical reactions have to be developed to modify GO/

rGO surfaces with desired functional groups before the grafting

of polymers. For example, after 4-bromophenyl groups were

coupled on the rGO surface through the diazonium reaction, a

fluorenethiophenebenzothiadazole polymer was covalently

grafted to the rGO surface through the Suzuki reaction via

the 4-bromophenyl groups.222 The pre-bonded diazonium

group on rGO can also act as the initiator for atomic transfer

radical polymerization (ATRP), based on which, PS has been

successfully grafted onto the rGO sheet with controlled

density.223 Additionally, acyl-chlorinated GO sheets can further

react and connect to triphenylamine-based polyazomethine

(TPAPAM)224 and MeOH-terminated P3HT,225 and the

APTES-modified GO surface can be further bonded with

maleic anhydride-grafted polyethylene (MA-g-PE).226

As shown in the aforementioned examples, the covalent

functionalization of polymers on graphene-based sheets holds

versatile possibility due to the rich surface chemistry of

GO/rGO. Nevertheless, the non-covalent functionalization,

which relies on the van der Waals force, electrostatic inter-

action or pp stacking,227 is easier to carry out without

altering the chemical structure of the capped rGO sheets,

and provides effective means to tailor the electronic/optical

property and solubility of the nanosheets. The first example of

non-covalent functionalization of rGO sheets was demonstrated

by the in situ reduction of GO with hydrazine in the presence

Fig. 4 (A) Schematic illustration of fabrication and assembly of the free-standing GO-LbL film. (B) Plot showing the variation of elastic modulus

calculated theoretically (under parallel and random orientation) and that obtained experimentally (using buckling and bulging measurements) with

the volume fraction of GO. Reproduced with permission from ref. 215. Copyright 2010, American Chemical Society.

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of poly(sodium 4-styrenesulfonate) (PSS),228 in which the

hydrophobic backbone of PSS stabilizes the rGO, and the

hydrophilic sulfonate side groups maintains a good dispersion

of the hybrid nanosheets in water. Later on, conjugated

polyelectrolytes with various functionalities have been usedto modify rGO nanosheets,14,17,41 in the hope to achieve good

solubility in different kinds of solvents, and at the same time

acquire added optoelectronic properties. Our group has

specially designed an amphiphilic coilrodcoil conjugated

triblock copolymer (PEGOPE, chemical structure shown in

Fig. 5A) to improve the solubility of graphenepolymer

nanocomposites in both high and low polar solvents.14 In

the proposed configuration, the conjugated rigid-rod back-

bone of PEGOPE can bind to the basal plane of the in situ

reduced GO via the pp interaction (Fig. 5B), whereas the

lipophilic side chains and two hydrophilic coils of the back-

bone form an amphiphilic outer-layer surrounding the rGO

sheet. As a result, the obtained rGO sheets with a uniformlycoated polymer layer (Fig. 5C) are soluble in both organic low

polar (such as toluene and chloroform) and water-miscible

high polar solvents (such as water and ethanol).

6. Other graphene-based composites

Other than inorganic nanostructures and polymers, materials

such as organic crystals,39,40 metalorganic frameworks

(MOF),4345 biomaterials,4648 and carbon nanotubes (CNTs)5053 have also been composited with graphene derivatives for

various applications.

For example, N,N0-dioctyl-3,4,9,10-perylenedicarboximide

(PDI)graphene core/shell nanowires have been prepared

through the pp interaction, and used in organic solar cells.39

Besides, peptidegraphene core/shell nanowires were prepared

by mixing graphene aqueous solution and the organic peptide

solution (diphenylalanine in 1,1,1,3,3,3-hexafluoro-2-propanol).

After removal of peptide cores by calcination, the hollow

graphene tubes were applied as supercapacitor electrodes.40

MOF, a recently emerging material, is promising in a

number of gas purification and storage based applications,

and has also been composited with GO/rGO sheets.4345 As an

interesting example, benzoic acid-functionalized graphene has

been found to act as a structure-directing template for the

growth of MOF-5, which exhibits the wire-like structure along

its [220] direction. Along the long axis of the wire, the

functionalized graphene sheets are periodically distributed,

which are expected to impart photoelectric transport property

to the insulating structure of MOF-5.43

Moreover, biomaterials like DNA hybridized with GO or rGO

are used in fluorescent sensing platforms based on the fluores-

cence resonance energy transfer (FRET),46,47 and biocompatible

aptamerGO composites can be applied in probing living cells.48

GrapheneCNT composites have also been prepared via solution

blending50,51 or in situ CVD growth53 to be applied in Li ion

batteries,51 transparent conductors,50 and supercapacitors.52,53

7. Applications of graphene-based composites

7.1 Lithium ion batteries

The increasing demand from the current information-rich

society to provide high efficient, low cost and green solutions

for energy conversion and storage devices, has been constantly

driving the development of battery systems, in particular, the

rechargeable batteries. Li ion battery (LIB) is considered as

one of the most promising storage systems, because of itshigh absolute potential against the standard hydrogen cell

(3.04 V) and its low atomic weight (M = 6.94 g mol1),

which leads to the large energy density with a theoretical value

of up to B400 Wh kg1.229,230 In addition to the traditional

insertion-type (e.g. TiS2 and LiCoO2)231,232 and alloying-type

(e.g. Sn)233 of electrode systems for insertion/extraction of Li,

the conversion-type LIB has been intensively studied recently,

which employs transition metal compounds (MaXb, M = Co,

Ni, Fe, Cu etc.; X = O, S, P , N etc.) to facilitate the Li

insertion/extraction through redox reactions (reaction (1))

between the ionic and metallic states of the metal, thus

providing high capacities.234

MaXb + cLi+ + ce2 LicXb + aM (1)

7.1.1 Graphenemetal oxide nanostructures for LIBs. The

nanostructured MaXb has been proven to be advantageous

compared to micrometre-sized structures for LIBs, owing to

the shortened diffusion length for both Li ions and electrons,

and larger specific surface area for the electrode/electrolyte

interaction.235 However, drawbacks like poor conductivity,

low packing density thus reduced volumetric energy density, as

well as the expansion induced lose of contact points, remain

problematic and require continuous development. Although

graphene and its derivatives cannot effectively host Li via

intercalation like in bulk graphite, they are able to store Li

through the surface absorption and functional groups induced

bonding,236 and they possess high conductivity and large

surface area. Therefore, many metal oxide nanostructures, like

SnO2,166,167,237 Co3O4,

54,55 MnO2,56 TiO2,

157,238 Fe3O4173 and

Cu2O,177 have been composited with graphene for LIBs.

Rapid capacity decay is usually observed in the pure metal

oxide based anodes, due to problems like poor conductivity,

structure degradation and expansion, and inter-particle

agglomeration. Using graphene based materials as matrices for

in situ synthesis and anchoring of the metal oxide nanostructures

is anticipated to solve these problems. First of all, the incorpora-

tion of graphene maintains a good conducting network in the

Fig. 5 (A) Chemical structure of PEGOPE. (B) Schematic illustra-

tion of fabrication of PEGOPE stabilized rGO sheets. (C) Tapping-

mode AFM image and cross-sectional analysis of PEGOPErGO on

mica. Reproduced with permission from ref. 14. Copyright 2010,

John Wiley & Sons, Inc.

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hybrid electrode. This effect has been elucidated in a recent report

on the Mn3O4/graphene based anode.56 Although Mn3O4

is an attractive anode material for LIBs considering its low

cost, abundance, and high theoretically value in capacity

(B936 mAh g1), its low conductivity (B 107108 S cm1)

has limited its practical application with a measured capacity of

400 mAh g1.56 Direct growth of Mn3O4 NPs on graphene

sheets provides a good contact between the NPs and the 3D

network of graphene, thus realizes efficient conduction of charge

carriers. Consequently, the graphene/Mn3O4 hybrid anode

affords a specific capacity of B900 mAh g1, about two times

higher than that by using the pure Mn3O4. The same effect,

arising from the conducting network of graphene sheets, has also

been demonstrated in SnO2/graphene,237 TiO2/graphene

157 and

Fe3O4/graphene173 electrodes.

By using graphene as templates, another attractive aspect is

that the synthesized NPs can be evenly distributed on the

graphene surfaces. In this way, the agglomeration of NPs can

be considerably reduced and the large active surfaces of the

NPs are able to participate in Li/electron diffusion more

efficiently during the discharge/charge cycles. As a result,

enhanced specific capacity and cycling performance have

been achieved in systems like Co3O4/graphene54 and Cu2O/

graphene177 composites. In addition, the elastic and flexible

graphene sheets can accommodate the volume expansion of

the NPs upon Li insertion/extraction; whereas the NPs in turn

prevent the re-stacking of the graphene layers.173 More

importantly, it has been shown that the structure integrity of

the crystalline NPs on graphene can be maintained after many

cycles of discharge/charge. As an example, the Li insertion/

extraction in SnO2 based anode usually involves a two phase

process, i.e. in the first cycle, the SnO2 reacts with Li+ to give

Sn and Li2O; after that, Sn will not reverse back to SnO2 but

form SnLix alloy for the rest cycles,237,239 which leads to large

volume change and rapid capacity decay. This problem can be

overcome by using SnO2/graphene hybrid anode, which shows

a well maintained SnO2 crystalline structure after 50 cycles.167

Although the graphene-based 2D templates have provided

the good NP distribution on individual sheets, the graphene

NP hybrid sheets are randomly stacked to make electrodes,

inevitably leading to the particleparticle aggregation. Thus,

the ordered graphenemetal oxide composites166 and graphene

encapsulated metal oxide nanostructures55 have been developed

to further reduce the particle aggregation. In the former case,

layers of graphene stacks and metal oxide NPs (e.g. SnO2) are

assembled alternatively through a surfactant assisted self-

assembly process (Fig. 2 in section 4.2.7). Such highly ordered

and stable structure of graphene/SnO2 exhibits a specific

energy density of B760 mAh g1, which is comparable to

the theoretical value for SnO2 without significant charge/

discharge degradation.166 However, most graphene stacks

consist of multi-layer graphenes, which reduce the useful

surface area of graphene and increase the carbon content in

the composite. In an alternative approach, graphene sheets are

made to wrap around NPs of SiO2 or Co3O4 via the electrostatic

interaction in the graphene encapsulated-metal oxide hybrids

(Fig. 6A).55 The graphene encapsulation is able to separate

individual NPs from one another, which prevents the particle

agglomeration, and maintains a conducting network to

effectively connect all NPs. The resulting graphene/Co3O4 based

anode, with a low carbon content ofo8.5 wt%, displays a very

high capacity of 1100 mAh g1 in the first 10 cycles, and

maintains at above 1000 mAh g1 even after 130 cycles (Fig. 6B).

7.1.2 Graphenecarbon nanotube or graphenefullerene

hybrid for LIB. To date, besides the graphenemetal oxide

based anode materials for LIBs, graphenecarbon nanotube

(CNT) or graphenefullerene (C60) hybrid electrodes are also

reported.51 The graphene nanosheets (GNSs), prepared from

reduction and re-assembly of oxidized GO sheets, consist of

615 re-stacked individual graphene monolayers. The GNSs

show a specific capacity ofB540 mAh g1, which is much

larger than that of graphite due to the enlarged specific surface

area after exfoliation. The energy storage property of this

electrode can be further improved by mixing GNSs with

nanocarbons, such as CNTs and C60, to increase the spacings

among the re-stacked GNSs. In this way, the additional voidsfor Li insertion/extraction are created in the mixtures, resulting

in B40% increase in the specific capacity.

7.2 Supercapacitors

Supercapacitor, or ultracapacitor, is another type of electro-

chemical energy storage device, which provides high power

density (10 kW kg1), short charge/discharge time (in seconds),

and long cycling life, as compared to the battery device.240

Thus, supercapacitor is widely applied for powering the heavy

vehicles, portable media players, personal computer (PC)

cards, and so on. Generally, there are two types of

Fig. 6 (A) Schematic illustration of fabrication of graphene-

encapsulated metal oxide NPs. (B) Cycle performance of graphene-

encapsulated Co3O4. Reproduced with permission from ref. 55.

Copyright 2010, John Wiley & Sons, Inc.

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supercapacitors, in terms of their operation mechanisms.241 One

is the electrical double layer capacitor (EDLC), which stores

energy via an electrostatic process, i.e. the charges are accumu-

lated at the electrode/electrolyte interface through polarization.

Hence, it is essentially important to use electrode materials with

good conductivity and large specific surface areas in EDLCs,

such as the activated carbon, CNTs, carbon nanofibers, and the

emerging graphene-based 2D sheets. The graphene-based

materials, in particular rGO, are advantageous in terms of the

chemically active surface with large specific area, good con-

ductivity, low cost, and mass production with solution-based

processability as mentioned before. In addition, it is suggested

that the aggregated graphene sheets exhibit an open-pore

structure, which allows for the easy access of electrolyte ions

to form electric double layers.242 The first EDLC based on the

chemically modified graphene, or rGO, was demonstrated by

Ruoff and coworkers.2 A specific capacitance of 135 F g1 in

the aqueous electrolyte is obtained, which is comparable with

the traditional carbon-based electrode materials.

The other type of supercapacitor is so called the pseudo-

capacitor, which is based on the rapid redox reactions of the

chemical species present in the electrode.241 Commonly used

electrode materials are metal oxides (e.g. RuO2, NiO and

MnO2) and conducting polymers (e.g. Polyaniline, PANi and

Polypryrrole, PPy). This type of electrode affords higher

specific capacitance per unit surface area (1 to 5 F m2)

compared to the porous carbon based EDL electrode (0.1 to

0. 2 F m2).242 However, the relatively high cost and low

conductivity of metal oxides or conducting polymers have

limited their applications. As a result, graphene derivatives

and metal oxides or conducting polymers are combined and

used as the hybrid type of supercapacitor (i.e. the combination

of the EDLC and pseudo-capacitor).

7.2.1 Graphenemetal oxide supercapacitors. A number of

metal oxides, such as ZnO,57 SnO2,58 Co3O4,

170 MnO2168,169

and RuO2,59 have been composited with graphene derivatives

to prepare electrodes for supercapacitors. Taking the

graphene/MnO2 hybrid electrode for example,169 the MnO2

NPs contribute to the energy storage via the redox reaction in

between the III and IV oxidation states of Mn (reaction (2)),

which involves the intercalation of alkali metal ions present in

the electrolyte, e.g. Na+. The rGO sheets, on the other hand,

provide the capacitance through the electron double layer

at the carbon surface, and meanwhile afford a conducting

network for the anchored MnO2 NPs and large surface area

for the NP/electrolyte interaction, which leads to high pseudo-

capacity with rapid chargedischarge rate. The resulting

composite electrode shows a high specific capacitance of

310 F g1 at 2 mV s1 (228 F g1 at even 500 mV s1), about

3 times higher than that given by the pure rGO or MnO2.

Similarly, a graphene nanosheet (GNS)/Co3O4 supercapacitor

displays a maximum specific capacity of 243.2 F g2 at a scan

rate of 10 mV s1 in KOH aqueous solution, and B95.6% of

the specific capacitance is retained after 2000 cycles.170

MnO2 + C+ + e2 MnOOC (2)

where C+ = Na+, K+ or Li+

Compared to batteries, supercapacitors exhibit higher

power density but lower energy density. In order to improve

the energy density of a supercapacitor, while maintaining the

high power density from the graphene/metal oxide hybrid elec-

trode, an asymmetric capacitor system was employed by Cheng

and coworkers.243 In such a capacitor, graphene is incorporated

as the negative electrode (a battery type) and MnO2

nanowire/

graphene composite (MGC) as the positive electrode (Fig. 7A).

A high operating voltage (B2.0 V) is thus made possible in this

asymmetric set-up to give the high energy density (note that the

energy is directly proportional to the square of the operating

voltage across the cell). As a result, a maximum energy density of

30.4 Wh kg1 for this asymmetric capacitor is achieved, which is

much higher than the results obtained from the symmetric one,

i.e. with graphene (or graphene/MnO2) as both the positive and

negative electrodes (Fig. 7B).

7.2.2 Graphene-conducting polymer supercapacitors. Con-

ducting polymers are attractive materials for supercapacitor

electrodes, because they have moderate conductivity, e.g.

0.15 S cm1 for doped polyaniline (PANi),244 fast chargedischarge kinetics and dopingundoping processes,245

and flexibility for thin film based fabrications.246 The power

conversion and storage process in polymer-based capacitors

involves the dopingundoping redox reactions, as shown in

reactions (3) and (4):

Cp + nA2 Cpn+(A)n + ne (p-doping) (3)

Cp + ne + nC+2 Cpn(C+)n (n-doping) (4)

where Cp = conducting polymer; C+ = cation; A = anion.

Fig. 7 (A) Schematic of the assembled structure of asymmetric ECs based on MGC as the positive electrode and graphene as the negative

electrode. (B) Ragone plot related to energy and power densities of graphene//MGC asymmetric ECs with various voltage windows, graphene//

graphene and MGC//MGC symmetric ECs. Reproduced with permission from ref. 243. Copyright 2010, American Chemical Society.

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Till now, PANi is one of the most employed polymers

to be incorporated with GO or rGO sheets for super-

capacitors.195,202207,247,248 In the GOPANi composite, the

doping process is realized by linking the carboxyl group of GO

to the nitrogen of the PANi backbone.205,206 Since PANi is

synthesized on GO via the in situ polymerization, the oxygen-

containing functional groups of GO can facilitate the nuclea-

tion of the polymer and give rise to good surface coverage of

PANi and the strong pp interaction between the PANi

backbone and the GO surface. As reported, with 1% mass

loading of GO, the conductivity of the PANi based electrode

is improved from 2 S cm1 (for pure PANi) to 10 S cm1, and

a high specific capacitance of 531 F g1 (216 F g1 for the pure

PANi) is obtained in the potential range of 0 to 0.45 V at a

scan rate of 10 mV s1.206 Besides the enhanced conductivity

and capacitance, GO is also able to improve the cycling-

stability of the composite electrode, because the flexible GO

sheets can undertake mechanical deformation during the

chargedischarge cycles to protect the PANi polymer from

shrinkage and swelling.205,248 For example, a hierarchical

composite electrode of GOPANi can retain 92% of the

initial capacitance after 2000 cycles, whereas the initial capa-

citance of pure PANi electrode drops to 74%.248

Although the chemically modified graphene, or rGO,

exhibits much better intrinsic conductivity as compared to

GO, the rGOPANi electrode has not shown any improved

electrochemical performance compared to GOPANi at a low

GO/rGO content (o 20 wt%).195,203 This is possibly because,

the less amount of oxygenated functional groups on the

surface of rGO compared to GO has caused the poor poly-

merization and distribution of PANi nanostructures, and less

effective doping of PANi via the carboxyl groups.

7.2.3 Graphenecarbon nanotube (CNT) supercapacitors.

In graphene-based supercapacitors, re-stacking of graphene

sheets can lead to the decrease of active surface area. To solve

this problem, CNTs can be used as spacers to create nanopores

among graphene layers, and at the same time provide good

conductivity. For example, poly(ethyleneimine) (PEI)-modified

rGO sheets mixed with acid-oxidized multi-walled CNTs to

make hybrid carbon films gave an average specific capacitance

of 120 F g1 at a high scan rate of 1 V s1.52 The concept of

using CNT spacers is further employed in a three dimensional

(3D) CNT/graphene sandwich structure (CGS), in which

CNTs are grown amongst the graphene layers via the

CVD process (Fig. 8A and B).53 The resulting Brunauer

EmmettTeller (BET) surface area of the CGS is 612 m2 g1,

which is much higher than that of graphene (202 m2 g1).

A specific capacitance of 386 F g1 is thus obtained at a scan

rate of 10 mV s1. The capacitance increases for ca. 20%

compared to the initial value after 2000 cycles (Fig. 8C),

suggesting the excellent electrochemical stability of the hybrid

carbon electrode.

7.3 Fuel cells

Unlike batteries or supercapacitors, which store energy

chemically in the electrochemical cells, the fuel cell generates

electricity via reactions between a fuel (anode) and an oxidant

(cathode), which are continuously supplied from external

sources. There are several different combinations of the fuel

and oxidant, with typical examples including the hydrogen/

oxygen cell and the methanol/oxygen cell. Pt-based catalysts

are the most popular materials used for low-temperature fuel

cells, e.g. the oxidation of hydrogen, methanol, or reformate.249

Since Pt is very expensive, Pt loading must be minimized, but

the fuel cell performance cannot be compromised. Therefore,

carbon-based catalyst supports, such as carbon black, CNTs

and graphene, are used to provide good dispersity and thus

large effective surface area of the supported catalyst particles.

GraphenePt composites have been attempted in the fuel cells,

such as the methanol oxidation cells6062,250252 and the

oxygen reduction cells.63,253,254

Enhanced electrocatalytic activity in methanol oxidation

has been obtained in graphene-supported Pt catalysts as

compared to the commercial carbon black (Vulcan XC-72)

supported Pt NPs.60,61 The superior performance arises from

the large specific surface area of graphene and its high

conductivity for electron and ion transport. Graphene has

also shown advantages compared to the CNT-based catalyst

support. First, the 2D configuration of graphene sheets with

both sides exposed to the solution, leading to larger active

surface area compared to the 1D tube structures. Second, due

to the large curvature of the CNT walls, the deposited Pt

particles are sometimes aggregated, and not as uniformly

distributed as on graphene-based supports.250 Moreover, it is

demonstrated that the chemically converted graphene, or

rGO, displays better tolerance towards CO poisoning during

the methanol oxidation compared to CNTs, because the

residual oxygenated functional groups of rGO can react

and remove the carbonaceous species.250 In a recent report,

Yoo et al. found that graphene nanosheets (GNS) are able to

assist the formation of Pt clusters with a size of B0.5 nm,251

and because these clusters are well distributed on the GNS

surface, their aggregation into larger Pt particles is avoided.

Fig. 8 (A) Schematic illustration of the formation of hybrid materials

with CNTs grown in between graphene nanosheets, showing stacked

layers of GO (left), catalyst particles adhered onto layer surface after

deposition (middle), and CNTs in between graphene layers after

growth (right). (B) SEM image of the CGS sheet. (C) Variations of

specific capacitance versus the cycle number measured at a scan rate of

200 mV s1 in 6 M KOH within the potential range from 0.2 to

0.45 V (versus saturated calomel electrode (SCE)). Reproduced with

permission from ref. 53. Copyright 2010, John Wiley & Sons, Inc.

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In addition, based on a theoretical study, surface defects and

voids on the graphene surface can enhance the interaction

between the graphene and anchored Pt or Au clusters.255

Consequently, these sub-nanometre Pt clusters can remain

stable on GNS even after the heat treatment at 400 1C in an

Ar/H2 environment. The resulting PtGNS hybrid catalyst

shows unusually high activity for methanol oxidation, e.g. the

PtGNS exhibits a current density of 0.12 mA cm2 at 0.6 V

(versus reference hydrogen electrode), about 3 times higher

than that obtained with the Ptcarbon black catalyst.

Nitrogen-doped graphene sheets, with better conductivity

compared to un-doped ones,256 have also been used as catalyst

supports in fuel cells.62,63 The N-doped rGO can be prepared

by nitrogen plasma treatment of rGO,63 or thermal reduction

of GO in the presence of ammonia (NH3),62 which gives rise to

nitrogen species on the carbon basal plane, such as amino,

pyridine and graphitic type groups. The presence of the

nitrogen species results in a good coverage and dispersion of

the in situ synthesized Pt NPs compared to the un-doped rGO

surface. This advantage along with the N-doping induced

increase of the electronic conductivity256 has led to much

enhanced electrocatalytic activities of N-rGOPt catalysts.62,63

For example, in a methanol fuel cell, the N-doped rGOPt

catalyst exhibited an oxidation current of 135 mA mg1, which

is 2 times higher than that of the rGOPt catalyst.62

7.4 Photovoltaic devices

A photovoltaic device converts the solar energy into electricity.

Besides the widely commercialized Si based solar cells, cheap

and efficient alternatives, such as the polymer based solar cells,

dye (or quantum dots, QD) sensitized solar cells, have also

been intensively investigated. The following context will

discuss the incorporation of graphene into these devices.

7.4.1 Silicon based solar cells. In order to partially replace

silicon, thus reducing cost in solar cell devices, carbon based

materials have been attempted in the p-type amorphous

carbon/n-type silicon (p-AC/n-Si) heterojunctions,257 and

CNT/Si heterojunctions.258 However, amorphous carbon

usually encounters difficulties in tuning its electronic properties,

while the CNT-based thin film suffers from bundling and thus

reduces the film connectivity and conductivity. In contrast,

graphene-based films can be prepared with controlled thick-

ness, good surface continuity, and tunable properties via

doping, covalent or non-covalent functionalizations. CVD-

grown graphene sheets with sizes of tens to hundreds micro-

metres have been deposited on n-Si with 100% coverage to

make the Schottky junction solar cell,64 which shows an

efficiency (PCE, Z) of up to B1.5% with a fill factor

of B56% (FF, actual obtainable maximum power vs. the

theoretical power). In addition to its low cost, the graphene

film serves as a semitransparent electrode and an antireflection

coating for the graphene/n-Si solar cells, and helps to generate

a built-in voltage of 0.550.57 V for the effective electron-hole

separation.64,259 Although the obtained efficiency is still lower

than that of pure Si-based solar cells, it is suggested that the

efficiency can be increased in future by improving the

conductivity and transparency of the graphene film.64

Additionally, the tunable work function of the graphene layer

affords the additional advantage to the graphene/silicon solar

cells, since a desirable work function allows for the efficient

carrier injection at the interface. One way to adjust the work

function of the graphene film is through controlling the layer

number of the graphene sheets via the LbL deposition,260

which has shown a sequential increase in work function with

increasing layer numbers. Another effective way to control the

work function is via chemical doping, e.g. Au-doping through

the electrochemical deposition.261 The resulting Au-doped

graphene films exhibit a change in work function of up to

B0.5 eV (i.e. from 4.66 eV to 3.96 eV), which leads to more

than 40 times increase in PCE as compared to the un-doped

graphene films.

7.4.2 Polymer based solar cells. In polymer-based hetero-

junction solar cells, graphene-based materials have been compo-

sited and incorporated to function as the electrodes,19,33,217,262264

electron transporters/acceptors,225,265267 and hole transporters.218

a. Transparent electrodes. Graphene thin films with easy

accessibility, good flexibility and transparency have shown

promises to replace indium tin oxide (ITO) as the transparentelectrode for solar cells and other electronic devices. In a

typical fabrication process, GO solutions are spin-coated on

quartz substrate and reduced chemically followed by high

temperature annealing. Additional layers in the device con-

figuration are deposited on top of the rGO film in sequence to

give the organic (e.g. quartz/rGO/P3HT/PCBM/PEDOT:PSS/

LiF/Al)217 or organic/inorganic hybrid (e.g. quartz/rGO/ZnO/

P3HT/PEDOT:PSS/Au)19 photovoltaic devices (Fig. 9A).

High temperature annealing not only improves the conductivity

of the rGO film,217,264 but also increases the work function of

rGO, resulting in a better match between the Fermi-level of the

rGO layer and the conduction band of the adjacent

Fig. 9 (A) Schematic illustration of the rGO thin film used as the

transparent electrode in a ZnO/P3HT hybrid solar cell. Reproduced

with permission from ref. 19. Copyright 2010, John Wiley & Sons, Inc.

(B) Schematic illustration of the P3HT/graphene hybrid film used as

the electron transport/acceptor layer in a polymer solar cell. Repro-

duced with permission from ref. 267. Copyright 2009, John Wiley &

Sons, Inc. (C) Left: schematic illustration of GO used as the hole

transport layer in a polymer solar cell. Right: Currentvoltage

characteristics of photovoltaic devices with no hole transport layer

(curve labeled as ITO), with a 30 nm PEDOT:PSS layer, and a 2 nm

thick GO film. Reproduced with permission from ref. 218. Copyright

2010, American Chemical Society.

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semiconducting layer for efficient charge injection.19 Besides

the work function, another key concern for the rGO electrode

is the transmittance. It is found that there exists a critical value

for the transmittance of the rGO electrode (e.g. 65%

in a device with a configuration of rGO/PEDOT:PSS/

P3HT:PCBM/TiO2/Al),33 above which the performance of

the device mainly depends on the charge transport efficiency

through the rGO electrodes, and below which the performance

is dominated by the light transmission efficiency. In addition

to rGO films, CVD-grown graphene films with better electrical

conductivity have also been used as the transparent electrode.

The performance of the CVD-grown graphene anode can

be improved by modulating its work function through

chemical means such as ozone treatment or non-covalent

functionalization.262 In the former approach, although ozone

treatment can generate the OH and CQO groups on the

graphene surface, thus improving the open circuit voltage

(Voc) and PCE, the electronic conductivity is compromised

due to the disrupted sp2 n

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